JP2013006893A - High thermal conductivity resin composition, high thermal conductivity cured product, adhesive film, sealing film, and semiconductor device using them - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a high thermal conductivity resin composition which has high thermal conductivity and excels in adhesion and reliability, and to provide an adhesive film, and a sealing film.SOLUTION: The high thermal conductivity resin composition at least includes: (1) a high thermal conductivity particle; (2) a thermosetting epoxy resin composition that contains an epoxy resin monomer with mesogen and an epoxy resin-curing agent ; and (3) a high molecular weight component of at least 10,000 of a weight average molecular weight, wherein (2) the thermosetting epoxy resin composition and (3) the high molecular weight component perform phase separation after curing. In addition, the adhesion film and the sealing film are configured by forming the high thermal conductivity resin composition into a film shape; and the semiconductor device is configured by laminating one or two chosen from the group consisting of a semiconductor element, a substrate, a radiator plate, a supporting body, a metal plate and a ceramic plate to a semiconductor element through the adhesive film or the sealing film.

Description

  The present invention relates to an adhesive film and a sealing film used for a semiconductor device, and a high thermal conductive resin composition used for producing them.

  Film type adhesives are used in flexible printed wiring boards and the like, and a system mainly composed of acrylonitrile butadiene rubber is used.

  What improved moisture resistance as a printed wiring board related material is an adhesive resin containing an acrylic resin, an epoxy resin, a polyisocyanate, and an inorganic filler disclosed in Patent Document 1, and an acrylic resin disclosed in Patent Document 2. In addition, there is an adhesive film in which both ends having an epoxy resin and a urethane bond in the molecule contain a primary amine compound and an inorganic filler. The adhesive film did not contain a filler having excellent thermal conductivity, and the thermal conductivity of the resin was low. Therefore, the thermal conductivity was low. Therefore, the addition of a filler having excellent thermal conductivity to the adhesive film is considered to increase the thermal conductivity. However, the fluidity decreases, the film strength, the action of relaxing the thermal stress, the heat resistance and the moisture resistance. There is a problem such as a decrease, and since it cannot be added in a large amount, there is a limit to improving the thermal conductivity.

  In addition, a mixture in which a large amount of highly heat-conductive inorganic particles are added to the resin has been proposed, but there is a resin with low thermal conductivity between the highly heat-conductive inorganic particles. There is a problem that the conductivity is low and the cost is disadvantageous and the moldability is also poor.

  Here, when the adherend is in contact with both sides of the adhesive film, the adherend is in contact with only one side, the one side is in contact with the outside such as the atmosphere, or in some cases there is no adherend or the area of the adhesive film There are cases where any of the above is true for each part. Of these, when the adherend is in contact with only one surface and the one surface is in contact with the outside, such as the atmosphere, the surface is sealed, protected, or covered, and this is sometimes called a sealing film.

  On the other hand, downsizing and weight reduction of electronic devices have been promoted in the past. As a result, high-density mounting on substrates has been required, and semiconductor packages mounted on electronic devices have become smaller, thinner and lighter. It has been. Conventionally, there are packages called LOC (Lead On Chip), QFP (Quad Flat Package) and the like, and CSP (Chip Size Package) and μBGA (Ball Grid) which are further downsized and lighter than packages such as LOC and QFP. Array) and the like are being developed. Recently, flip-chips and wafer level CSPs, which are so-called face-down packages, in which the circuit surface of a semiconductor element is directed to the semiconductor wiring substrate side have been developed.

  In the above-described package, a sealed package is obtained by molding a solid epoxy resin sealing material by a transfer molding method. However, molding when the package is thin or large is difficult. In addition, when the content of the inorganic filler increases, the melt viscosity at the time of transfer molding generally increases, resulting in a decrease in the quality of the molded product, such as residual voids in the molded product, poor filling of the cavity, increased wire flow and stage shift. Problems occur.

  In recent years, some flip-chips, wafer level CSPs, and the like have protruding electrodes, and a sealant is sometimes used to protect the protrusions and to fill the protrusions. Molding with a stopper was difficult. Therefore, a film-like sealing sheet mainly composed of an epoxy resin and an inorganic filler has been proposed. The film-like sealing sheet has problems such as an increase in warpage when a package or a wafer becomes large, and a sealing film having a smaller linear expansion coefficient has been desired. Usually, in order to reduce the linear expansion coefficient, a large amount of an inorganic filler such as silica having a smaller linear expansion coefficient than that of the resin is filled, but this method reduces the flexibility of the film. In addition, there is a problem that the melt viscosity is increased and the fluidity is also decreased. Until now, a sealing film having high flexibility, high fluidity, low melt viscosity and low linear expansion coefficient, and excellent thermal conductivity has not been obtained. For example, although there is a sealing film shown in Patent Document 3, it did not have a particularly excellent heat dissipation.

JP-A-60-243180 JP-A-61-138680 Patent No. 4225162

The present invention has been made in view of the above-described conventional problems, and an object thereof is to achieve the following object.
That is, the object of the present invention is that the flexibility and fluidity are large in the B-stage state, the linear expansion coefficient is small after curing, the thermal conductivity is excellent, and the semiconductor element surface protection characteristics are excellent. High thermal conductive resin cured product, adhesive film or sealing film, high thermal conductive resin composition capable of producing them, and use of the adhesive film and / or sealing film, thermal conductivity, assembly processability, reliability An object of the present invention is to provide an excellent semiconductor device.

The present invention for solving the above problems is as follows.
(1) 1) high thermal conductivity particles, 2) a thermosetting epoxy resin composition comprising an epoxy resin monomer having mesogen and a curing agent for epoxy resin, and 3) a high molecular weight component having a weight average molecular weight of 10,000 or more. A high thermal conductive resin composition comprising:
The high heat conductive resin composition, wherein the 2) thermosetting epoxy resin composition and the 3) high molecular weight component are phase-separated after curing.

(2) The high thermal conductive resin composition according to (1), wherein the epoxy resin monomer is an epoxy resin monomer represented by the following general formula (1).
E-MS-ME ... General formula (1)
(However, E represents an epoxy group, M represents a mesogen, and S represents a spacer portion)

(3) The 3) high molecular weight component is dissolved with the 2) thermosetting epoxy resin composition before curing, and has a glass transition temperature of 30 or more with a weight average molecular weight of 10,000 or more that phase-separates into an island shape after curing. A high molecular weight component of ℃ or less,
Said 1) high thermal conductivity particle is 40-90 volume% of the whole, and said 3) 5-50 mass parts of said high molecular weight component is contained with respect to 100 mass parts of thermosetting epoxy resin composition. The high thermal conductive resin composition according to (1) or (2), wherein

(4) The high thermal conductive resin composition according to any one of (1) to (3), further comprising a pigment, a dye, and a compound that absorb laser light.

(5) A cured resin product obtained by curing the thermosetting resin composition according to any one of (1) to (4),
It has an anisotropic structure consisting of a crystal phase or a liquid crystal phase, the maximum value of the diameter of the anisotropic structural unit is 400 nm or more, and the proportion of the anisotropic structure contained in the resin component is 25% by volume or more. A cured product of high thermal conductive resin, characterized by

(6) An adhesive film formed by molding the high thermal conductive resin composition according to any one of (1) to (4) into a film shape.

(7) An adhesive film obtained by applying pressure in the thickness direction to the adhesive film according to (6).

(8) An adhesive film, which is cooled after applying pressure to the adhesive film according to (7) under heating by pressing or roll processing.

(9) A sealing film formed by molding the high thermal conductive resin composition according to any one of (1) to (4) into a film shape.

(10) A sealing film obtained by applying pressure in the thickness direction to the sealing film according to (9).

(11) A sealing film, wherein the sealing film according to (9) is cooled after being heated under pressure by pressing or roll processing, and then cooled.

(12) The high thermal conductive resin composition according to any one of (1) to (4), the adhesive film according to any one of claims (6) to (8), and the (9) to (11) One type selected from the group consisting of a semiconductor element, a semiconductor element, a substrate, a heat sink, a support, a metal plate, and a ceramic plate via at least one of the sealing films according to any one of Alternatively, a semiconductor device characterized by stacking two kinds.

(13) The high thermal conductive resin composition according to any one of (1) to (4), the adhesive film according to any one of (6) to (8), and the above (9) to (11) A semiconductor device characterized in that at least one of the sealing films according to any one of the above is adhered or sealed to one or both sides of a semiconductor element.

  According to the present invention, in the B stage state, the flexibility and fluidity are large, the linear expansion coefficient is small after curing, and the thermal conductivity is excellent. Uses cured resin, adhesive film or sealing film, high thermal conductive resin composition capable of producing them, and the adhesive film and / or sealing film, and is excellent in thermal conductivity, assembly processability, and reliability A semiconductor device can be provided.

<High thermal conductive resin composition>
The high thermal conductive resin composition of the present invention includes 1) high thermal conductive particles, 2) a thermosetting epoxy resin composition containing an epoxy resin monomer having mesogen and a curing agent for epoxy resin, and 3) a weight average molecular weight of 10,000. A high thermal conductive resin composition containing at least the above high molecular weight component, wherein the 2) thermosetting epoxy resin composition and the 3) high molecular weight component are phase-separated after curing.
Hereinafter, each component of the highly heat conductive resin composition of this invention is explained in full detail.

1) High thermal conductivity particles The high thermal conductivity particles (hereinafter referred to as (A)) used in the present invention are not particularly limited as long as they are high thermal conductivity particles. For example, high thermal conductivity inorganic particles (hereinafter referred to as (a1) )); Coated particles obtained by coating inorganic particles with a high thermal conductive resin (hereinafter referred to as (a2)); and the like. In the case of expensive high thermal conductivity particles such as diamond, it is preferable to use the particles as coated particles (a2) coated with a high thermal conductivity resin in that the thermal conductivity can be improved with a minimum amount of use.
There is no restriction | limiting in particular in the shape of highly heat conductive particle | grains (A), For example, spherical shape, flat granular form, dendritic shape etc. are mentioned, Among these, spherical shape or flat granular shape is preferable.
In addition, the volume average particle diameter of the high thermal conductivity particles (A) (hereinafter sometimes simply referred to as “average particle diameter”) is not particularly limited, and is usually in the range of 0.05 to 55 μm. When the thickness of the adhesive film is a thin film of 20 μm or less, the average particle size is preferably 0.5 to 5 μm.

  When the high thermal conductivity inorganic particles (a1) are used as the high thermal conductivity particles (A), the thermal conductivity is preferably 30 W / mK or more, more preferably 100 W / mK or more, and particularly preferably 200 W / mK or more. . When the thermal conductivity is less than 30 W / mK, the heat dissipation is insufficient, and the temperature of the semiconductor element or the substrate may increase. The upper limit of the thermal conductivity is not particularly limited, but is usually 1100 W / mK or less. Specific examples of the high thermal conductivity inorganic particles (a1) include aluminum nitride, hexagonal boron nitride, cubic boron nitride, silicon nitride, diamond, alumina, and the like. You may use as a mixture of the above. The average particle size of the highly heat-conductive inorganic particles (a1) is preferably 0.05 to 50 μm.

  On the other hand, when the coated particles (a2) are used as the high thermal conductivity particles, the average particle size is not particularly limited, and is usually in the range of 0.06 to 55 μm, and the average particle size of the inorganic particles is 0.05 to 0.05. The thickness is preferably 50 μm, and the thickness of the high thermal conductive resin coating layer is preferably 0.01 to 5 μm.

  The thermal conductivity of the inorganic particles to be coated is not particularly limited, and the inorganic particles may be low thermal conductivity or high thermal conductivity. Specific examples of the low thermal conductivity inorganic particles include aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, aluminum borate whisker, crystalline silica, non-crystalline Examples thereof include crystalline silica and antimony oxide. Specific examples of the high thermal conductivity inorganic particles include the same as described above.

  There is no restriction | limiting in particular in the high heat conductive resin which coat | covers an inorganic particle. Examples of the high thermal conductive resin include, for example, a crystalline or liquid crystalline epoxy resin, a polyethylene resin, a polyester resin, nylon, a polyimide resin, and the like that themselves have a high thermal conductivity; an epoxy resin, a polyimide resin, etc. A resin composition obtained by blending high thermal conductivity particles and imparting high thermal conductivity is used. Among these, a resin composition obtained by blending high thermal conductivity particles such as alumina with an epoxy resin is preferable from the viewpoint of thermal conductivity. The high thermal conductive resin may be used in combination with a curing agent or a curing accelerator.

  Examples of the method of coating the inorganic particles with the high thermal conductive resin include a method of forming a vapor-deposited polymer film of the high thermal conductive resin on the surface of the inorganic particles; Therefore, a method of heating and drying while stirring and mixing; a method of stirring and mixing the high thermal conductive resin varnish and the inorganic particles, heating and drying, and crushing the adhered particles;

  The content of the highly thermally conductive particles (A) in the resin composition is preferably 40 to 90% by volume, more preferably 60 to 80% by volume. If the content of the high thermal conductive particles (A) is less than 40% by volume, the thermal conductivity of the adhesive film may be insufficient, and if it exceeds 90% by volume, the flexibility and adhesiveness of the adhesive film are deteriorated. there's a possibility that. In order to further improve the thermal conductivity of the adhesive film, in order to make the high thermal conductive particles (A) easily contact each other, the content of the high thermal conductive particles (A) is set to 65 to 75% by volume. More preferred.

2) Thermosetting epoxy resin composition containing an epoxy resin monomer having mesogen and a curing agent for epoxy resin The mesogenic group in the present invention indicates a functional group that may exhibit liquid crystallinity. Specific examples include biphenyl, phenylbenzoate, azobenzene, stilbene, and derivatives thereof.

  Moreover, the epoxy resin monomer in this invention shows the monomer which has an at least 1 epoxy group. Further, the epoxy resin monomer preferably has a mesogenic group in at least 5% of the weight ratio of all epoxy resins. Specific examples include an epoxy resin monomer having at least one mesogen such as a biphenyl group, a phenylbenzoate group, a stilbene group, and an azobenzene group, and a twin mesogen type epoxy resin monomer having two or more molecules in the molecule. .

As the epoxy resin monomer, an epoxy resin monomer represented by the following general formula (1) is particularly preferable. Such a twin mesogen type epoxy resin monomer is most preferable for improving the maximum value of the diameter of the anisotropic structural unit and the ratio of the anisotropic structure.
E-MS-ME ... General formula (1)
(However, E represents an epoxy group, M represents a mesogen, and S represents a spacer portion).

Here, the anisotropic structure in the present invention refers to a structure having a micro array. For example, a crystal phase or a liquid crystal phase corresponds. Whether or not such a structure exists in the resin can be easily determined by observation with a polarizing microscope. That is, in the observation in the direct Nicole state, it can be distinguished by the interference fringes due to the depolarization phenomenon.
This anisotropic structure is usually present in an island shape in the resin, and the anisotropic structural unit in the present invention is one of the islands. In the present invention, this anisotropic structural unit needs to have a covalent bond.

  The maximum value of the diameter of the anisotropic structural unit and the ratio of the anisotropic structure in the present invention can be calculated by directly observing with a transmission electron microscope (TEM).

The hardening | curing agent for epoxy resins in this invention points out the hardening | curing agent used in order to harden | cure an epoxy resin.
The curing agent used in the present invention is not particularly limited as long as it is a conventionally used known epoxy resin curing agent. For example, amines, polyamides, acid anhydrides, polysulfides, boron trifluoride, and phenolic hydroxyl groups can be used. Bisphenols such as bisphenol A, bisphenol F and bisphenol S, which are compounds having two or more in one molecule, phenol novolak resin, modified phenol novolak resin, resorcinol novolak resin, catechol resorcinol novolak resin, bisphenol A novolak resin or cresol novolak resin And phenolic resins. In particular, a phenol resin such as a phenol novolac resin, a bisphenol novolac resin, or a cresol novolac resin is preferable in terms of excellent electric corrosion resistance when absorbing moisture.

  Commercially available phenolic resins include Dainippon Ink and Chemicals, Inc., trade names: Barcam TD-2090, Barcam TD-2131, Pryofen LF2882, Pryofen VH4150, Pryofen VH4170, Phenolite LF2882, Phenolite LF2822, There are Mitsui Chemicals, Inc., trade name: Mirex XLC series, XL series, and the like.

The weight average molecular weight of the phenol resin is preferably 300 to 2000, 500
More preferably, it is ˜1500.

  In the epoxy resin curing agent, the total amount of reactive groups in the curing agent is preferably 0.6 to 1.4 equivalents, more preferably 0.8 to 1.2 equivalents with respect to 1 equivalent of epoxy groups of the epoxy resin. It mixes so that it may become. Even if the content of the curing agent is less than 0.6 equivalents or exceeds 1.4 equivalents, the heat resistance tends to decrease.

(Curing accelerator)
As the curing accelerator used in the present invention, for example, a quaternary phosphonium salt system, a quaternary ammonium salt system, an imidazole system, a DBU fatty acid salt system, a metal chelate system, a metal salt system, a triphenylphosphine system, or the like may be used. it can. Examples of imidazole-based curing accelerators include 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-phenylimidazolium trimellitate, and the like. As products, there are Shikoku Kasei Kogyo Co., Ltd., trade names: Curezol 2E4MZ, Curezol 2PZ-CN, Curezol 2PZ-CNS. In addition, latent curing accelerators are also preferably used in that the useful life of the adhesive film is increased. Typical examples thereof include dihydrazide compounds such as dicyandiimide and adipic acid dihydrazide, guanamic acid, melamic acid, epoxy compounds and imidazole. Examples include, but are not limited to, addition compounds with compounds, addition compounds of epoxy compounds and dialkylamines, addition compounds of amines and thiourea, addition compounds of amines and isocyanates, and the like. Those having an adduct type structure are particularly preferred in that the activity at room temperature can be reduced. Representative examples of adduct type curing accelerators are shown below, but are not limited thereto. As commercial products of amine-epoxy adduct type curing accelerators, Ajinomoto Co., Inc., trade names: Amicure PN-23, Amicure MY-24, Amicure MY-D, Amicure MY-H, etc., ARC Corporation Product names: Hardener X-3615S, Hardner X-3293S, etc., manufactured by Asahi Kasei Co., Ltd., trade names: Novacure HX-3748, Novacure HX-3088, etc., Pacific Anchor Chemical, trade names: Ancamine 2014AS, Ancamine 2014FG, and the like. Moreover, as a commercial item of an amine-urea adduct type hardening accelerator, the Fuji Chemical Co., Ltd. make, brand name: Fujicure FXE-1000, Fujicure FXR-1030, etc. are mentioned.

  The blending amount of the curing accelerator is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass with respect to 100 parts by mass of the total of the epoxy resin and the curing agent. If the blending amount of the curing accelerator is less than 0.1 parts by mass, the curing rate tends to be slow, and if it exceeds 20 parts by mass, the pot life tends to be short.

[Thermosetting resin]
In the present invention, in addition to the above-described thermosetting epoxy resin composition containing an epoxy resin monomer having a mesogen and a curing agent for an epoxy resin, a thermosetting resin having no mesogenic group is intended to improve fluidity and flexibility. It may be used in combination, and specific resin components include cured products such as unsaturated polyester resins, epoxy resins, acrylic resins, phenol resins, melamine resins, urea resins, and urethane resins. In particular, an epoxy resin having excellent insulating properties and heat resistance can be given. These resin components can contain a monomer, a crosslinking agent, a flexible agent, a diluent, a modifier, and the like. The epoxy resin is not particularly limited as long as it cures and exhibits an adhesive action, and a bifunctional or higher functional epoxy resin containing two or more epoxy groups in one molecule is preferable. The weight average molecular weight of the epoxy resin is preferably 300 or more and less than 5000, more preferably 300 or more and less than 3000, in order to keep the flexibility of the adhesive film good. In the present invention, the weight average molecular weight is measured by gel permeation chromatography using a standard polystyrene calibration curve.

  Examples of the bifunctional epoxy resin containing two epoxy groups in one molecule include bisphenol A type or bisphenol F type epoxy resin. Commercially available products of bisphenol A type or bisphenol F type epoxy resin are manufactured by Yuka Shell Epoxy Co., Ltd., trade names: Epicoat 807, Epicoat 827, Epicoat 828, Dow Chemical Japan Co., Ltd., trade name: D.C. E. R. 330, D.E. E. R. 331, D.D. E. R. 361, manufactured by Toto Kasei Co., Ltd., trade names: YD8125, YDF8170, and the like.

  Examples of the tri- or higher functional epoxy resin containing three or more epoxy groups in one molecule include phenol novolac type epoxy resins and cresol novolac type epoxy resins. Commercial products of phenol novolac type epoxy resins include Nippon Kayaku Co., Ltd., trade name: EPPN-201. Commercially available products of cresol novolac type epoxy resin are manufactured by Sumitomo Chemical Co., Ltd., trade names: ESCN-190, ESCN-195, Nippon Kayaku Co., Ltd., trade names: EOCN1012, EOCN1025, EOCN1027, manufactured by Toto Kasei Co., Ltd. Product names: YDCN701, YDCN702, YDCN700-11, and YDCN704.

  When using a bifunctional epoxy resin and a trifunctional or higher functional epoxy resin as the epoxy resin, the bifunctional epoxy resin is 50 to 100 mass% and the trifunctional or higher functional epoxy resin is 0 to 50 mass with respect to a total of 100 parts by mass. % Is preferably used. In particular, for high Tg, it is preferable to use 50 to 90% by mass of a bifunctional epoxy resin and 10 to 50% by mass of a trifunctional or higher functional epoxy resin.

  The curing agent is not particularly limited as long as it is a known epoxy resin curing agent as described above. For example, two amines, polyamide, acid anhydride, polysulfide, boron trifluoride, and phenolic hydroxyl group per molecule. Examples thereof include bisphenols such as bisphenol A, bisphenol F, and bisphenol S, phenol novolac resins, modified phenol novolac resins, phenol resins such as bisphenol A novolac resins and cresol novolac resins.

3) High molecular weight component The weight average molecular weight of the high molecular weight component used in the present invention is 10,000 or more, and 2) the thermosetting epoxy resin composition and 3) the high molecular weight component undergo phase separation after curing. When the weight average molecular weight is less than 10,000, the strength and flexibility when the resin composition is made into a film form tend to be lowered, or the tackiness tends to be increased. The weight average molecular weight is preferably 100,000 or more, more preferably 300,000 or more. In addition, as the weight average molecular weight increases, the flowability of the resin composition decreases and the filling performance of the wiring circuit tends to decrease. Therefore, the weight average molecular weight of the high molecular weight component is 2 million or less. Is preferable, and it is more preferable that it is 1 million or less. The weight average molecular weight is a value measured by gel permeation chromatography and converted using a standard polystyrene calibration curve.

  Further, the glass transition temperature (Tg) of the high molecular weight component is preferably less than 50 ° C. in order to maintain the flexibility of the adhesive film. The glass transition temperature is more preferably −50 ° C. or higher and 30 ° C. or lower, and particularly preferably −30 ° C. or higher and 15 ° C. or lower. When the glass transition temperature is less than −50 ° C., the tackiness of the adhesive film in the B-stage state tends to be increased and the handleability tends to deteriorate. When the glass transition temperature exceeds 30 ° C., the film tends to break when handled at room temperature. .

  The high molecular weight component is a high molecular weight component having a functional group in that the crosslinking reaction is likely to proceed and the adhesive strength is likely to decrease due to gelation in the varnish state and increase in the degree of cure in the B stage state. Is preferred. The functional group may be present in the polymer chain or at the end of the polymer chain. Examples of the functional group include an epoxy group, a carboxyl group, a hydroxyl group, an acryloyl group, a methacryloyl group, an isocyanate group, an amino group, and an amide group. Among these, an epoxy group is preferable.

  The amount of the functional group-containing monomer in the high molecular weight component is preferably 0.5 to 6.0% by mass, more preferably 1.0 to 4.0% by mass, based on the total monomer amount. When the amount of the functional group-containing monomer is less than 0.5% by mass, the heat resistance tends to decrease, and when it exceeds 6.0% by mass, the viscosity of the varnish tends to increase. When the viscosity of the varnish increases, it becomes difficult to form a film, so it is necessary to dilute with an appropriate amount of solvent for the purpose of reducing the viscosity, the solid content of the varnish decreases, the amount of varnish preparation increases, and the production efficiency decreases. Tend.

  Examples of the method for producing the high molecular weight component having a functional group include a method of polymerizing a polymerizable monomer having a functional group alone, a polymerizable monomer having a functional group, and other polymerizable monomers copolymerizable therewith. Can be obtained by a copolymerization method. The polymerization method is not particularly limited, and for example, methods such as pearl polymerization and solution polymerization can be used.

  As a preferred example of the high molecular weight component having a functional group, an epoxy group-containing monomer such as glycidyl (meth) acrylate and a monomer having an ethylenically unsaturated bond such as ethyl (meth) acrylate or butyl (meth) acrylate are used. As a commercial product, a product name: HTR-860P-3 manufactured by Teikoku Chemical Industry Co., Ltd. can be used.

  Since the high molecular weight component can be a thermal resistance in the film, the blending amount of the high molecular weight component is preferably 5 to 20 parts by mass with respect to 100 parts by mass of the total amount of the epoxy resin and the curing agent. In order to use for the expression of a high thermal conductivity or the protection of a chip or the like with a high elastic modulus, the blending amount is preferably 5 to 10 parts by mass. Further, the blending amount is preferably 10 parts by mass or more in order to reduce the elastic modulus and impart flowability during molding.

  In the high thermal conductive resin composition of the present invention, 2) a thermosetting epoxy resin composition and 3) a high molecular weight component undergo phase separation after curing. While the phase of the thermosetting epoxy resin composition plays the role of a heat-resistant reinforcing material, the phase of the high molecular weight component dispersed in a network exhibits stress relaxation properties. Therefore, it can be a soft and strong material. Moreover, the thermosetting epoxy resin composition and high molecular weight component before hardening are uniformly dissolved. Since the thermosetting epoxy resin component also acts as a plasticizer or tackifier, it is possible to adjust fluidity and adhesiveness by changing the amount of the epoxy resin component.

  From the viewpoint that the highly heat conductive resin composition of the present invention can exert its effect most, 3) the high molecular weight component is dissolved with the 2) thermosetting epoxy resin composition before curing, and is island-shaped after curing. Is a high molecular weight component having a glass transition temperature of 30 ° C. or less and a weight average molecular weight of 100,000 or more, and 1) high thermal conductivity particles are 60 to 80% by volume, and 2) thermosetting. It is preferable that 5-30 mass parts of said 3) high molecular weight components are contained with respect to 100 mass parts of a conductive epoxy resin composition.

[Pigments, dyes, compounds that absorb laser light]
The high thermal conductive resin composition of the present invention preferably contains a pigment, dye, or compound that absorbs laser light for laser marking. As such a material that absorbs laser light, for example, carbon black, graphite, titanium carbon, manganese dioxide, phthalocyanine-based pigments and dyes can be used.
In addition, the wavelength of the laser beam which the said pigment, dye, and compound absorb is a wavelength within the range of 300-1100 nm.

[Other ingredients]
The high thermal conductive resin composition of the present invention can contain a curing agent, a curing accelerator, a filler, a coupling agent, an ion scavenger and the like as other components.

(Filler)
In the present invention, for the purpose of improving the handleability of the resin composition, improving the thermal conductivity, adjusting the melt viscosity, imparting thixotropic properties, improving the moisture resistance, etc., other than the high thermal conductive particles (A) Various fillers may be blended, and these do not need to have a thermal conductivity of 30 W / mK or more. Such fillers include aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, aluminum borate whisker, crystalline silica, amorphous silica, and antimony. An oxide etc. are mentioned. Of these, crystalline silica and amorphous silica are preferred for improving thermal conductivity. For the purpose of adjusting melt viscosity and imparting thixotropic properties, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, crystalline silica, amorphous Silica and the like are preferable. In order to improve the moisture resistance, silica, aluminum hydroxide, and antimony oxide are preferable. The content of these fillers is preferably 0 to 50 parts by mass, more preferably 0 to 20 parts by mass, and particularly preferably 0 to 10 parts by mass per 100 parts by mass of the highly thermally conductive particles.

(Coupling agent)
The high thermal conductive resin composition of the present invention may contain a coupling agent in order to improve interfacial bonding between different materials. Examples of the coupling agent include a silane coupling agent, a titanate coupling agent, and an aluminum coupling agent, and among these, a silane coupling agent is preferable. It is preferable that the compounding quantity of a coupling agent is 0.1-10 mass parts with respect to the total amount of 100 mass parts of a resin composition from the point of the effect by addition, heat resistance, and cost.

  As the silane coupling agent, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-ureidopropyltriethoxysilane, N-β-aminoethyl-γ- Examples include aminopropyltrimethoxysilane. As a commercial item of the said silane coupling agent, the product name: NUC A-187 (γ-glycidoxypropyltrimethoxysilane), manufactured by Nippon Unicar Co., Ltd., product name: NUC A-189 (γ-mercaptopropyltri) Methoxysilane), trade name: NUC A-1100 (γ-aminopropyltriethoxysilane), trade name: NUC A-1160 (γ-ureidopropyltriethoxysilane), trade name: NUC A-1120 (N-β-) Aminoethyl-γ-aminopropyltrimethoxysilane).

(Ion scavenger)
The high thermal conductive resin composition of the present invention can contain an ion scavenger in order to adsorb ionic impurities and improve insulation reliability during moisture absorption. It is preferable that the compounding quantity of an ion trapping agent is 1-10 mass parts with respect to the total amount of 100 mass parts of a resin composition from the point of the effect by addition, heat resistance, and cost.

  As the ion scavenger, a compound known as a copper damage inhibitor, for example, a triazine thiol compound, a bisphenol-based reducing agent, an inorganic ion adsorbent, or the like can be used to prevent copper from being ionized and dissolved. As a copper damage inhibitor comprising a triazine thiol compound as a component, Sankyo Pharmaceutical Co., Ltd., trade name: Disnet DB is commercially available. Examples of the bisphenol-based reducing agent include 2,2′-methylene-bis- (4-methyl-6-tert-butylphenol), 4,4′-thio-bis- (3-methyl-6-tert-butylphenol). Yoshitomi Pharmaceutical Co., Ltd., trade name: Yoshinox BB is commercially available. Examples of the inorganic ion adsorbent include zirconium-based compounds, antimony bismuth-based compounds, magnesium aluminum-based compounds, and the like, and trade name: IXE manufactured by Toa Gosei Chemical Industry Co., Ltd. is commercially available.

<Hardened thermosetting resin>
The thermosetting resin cured product of the present invention is a resin cured product obtained by curing the thermosetting resin composition of the present invention described above, and has an anisotropic structure consisting of a crystal phase or a liquid crystal phase, The maximum value of the diameter of the anisotropic structural unit is 400 nm or more, and the ratio of the anisotropic structure contained in the resin component is 25% by volume or more.

In the thermosetting resin cured product of the present invention, the maximum value of the diameter of an anisotropic structural unit composed of a crystal phase or a liquid crystal phase is 400 nm or more, but if it is within this range, the thermal conductivity of the resin is improved. When the diameter of the anisotropic structural unit is less than 400 nm, the thermal conductivity of the resin rapidly decreases.
Moreover, although the ratio of the anisotropic structure contained in a resin component is 25 volume% or more, the heat conductivity of resin improves that it is the range. On the other hand, if the proportion of the anisotropic structure is 25% by volume, the thermal conductivity of the resin rapidly decreases. The proportion of the anisotropic structure is preferably 25% by volume, and more preferably 40% by volume.

  The high thermal conductive resin cured product of the present invention preferably has a storage elastic modulus at 25 ° C. measured by a dynamic viscoelasticity measuring device of 20 to 20000 MPa, particularly 100 to 20000 MPa. When the storage elastic modulus at 25 ° C. is less than 20 MPa, the handling property of the adhesive and the thickness accuracy of the adhesive layer tend to deteriorate, and when the storage elastic modulus at 260 ° C. is less than 3 MPa, reflow cracks tend to occur. . The high thermal conductive resin cured product of the present invention can be obtained, for example, by heating the above-described high thermal conductive resin composition of the present invention at 130 to 200 ° C. for 0.5 to 8 hours. The storage elastic modulus is measured using, for example, a dynamic viscoelasticity measuring device (DVE-V4, manufactured by Rheology), applying a tensile load to the cured product in the C stage state, a frequency of 10 Hz, and a temperature rising rate of 5 to 10. It can be measured by a temperature-dependent measurement mode in which measurement is performed from -50 ° C to 300 ° C at ° C / min.

<Adhesive film>
The adhesive film of the present invention is formed by molding the above-described highly heat conductive resin composition of the present invention into a film shape.

  The adhesive film of the present invention has high flexibility and fluidity in the B-stage state, has a low linear expansion coefficient after curing, and is excellent in thermal conductivity.

  The adhesive film of the present invention is obtained by applying a varnish of the highly heat conductive resin composition of the present invention containing high heat conductive particles and a thermosetting epoxy resin composition on the carrier film, and removing the solvent by heating, thereby removing the carrier film. It can be produced by forming a film thereon.

  It is preferable to apply pressure in the thickness direction to the adhesive film obtained as described above. By doing in this way, both surfaces of a film are planarized and the adhesive strength of a film can be improved.

  The heating conditions are not particularly limited as long as the solvent can be removed without completely curing the high thermal conductive resin composition of the present invention, and vary depending on the components of the resin composition and the type of the solvent. Generally, heating is performed at 80 to 140 ° C. for 5 to 60 minutes. It is preferable that the resin composition is cured to about B stage by heating. In the B stage film, by leaving a certain amount of the solvent, the tackiness and laminating properties of the film are improved. As a result, the adhesiveness after curing is improved, and the thermal resistance at the adherend interface is further reduced. Therefore, heat dissipation can be improved. The remaining amount of the solvent is preferably 0.1 to 20% by mass, more preferably 0.2 to 10% by mass, and particularly preferably 1 to 7% by mass with respect to the film. In addition, when it hardens | cures in the state in which the protective film remained, since a solvent is hard to evaporate, it will foam easily. After laminating a film or the like on an adherend such as a wafer, the protective film is preferably peeled off and cured.

  As the carrier film, polytetrafluoroethylene film, polyethylene terephthalate film, polyethylene film, polypropylene film, polymethylpentene film, polyimide film, polyethylene naphthalate film, polyethersulfone film, polyetheramide film, polyetheramideimide film Plastic films such as polyamide film and polyamideimide film can be used. If necessary, surface treatment such as primer coating, UV treatment, corona discharge treatment, polishing treatment, etching treatment, mold release treatment, etc. may be performed. As a commercial product of a carrier film, for example, Toray DuPont Co., Ltd., trade name: Kapton (polyimide film), Kaneka Chemical Co., Ltd., trade name: Apical (polyimide film), Toray DuPont Co., Ltd., Trade name: Lumirror (polyethylene terephthalate film), manufactured by Teijin Limited, trade name: Purex (polyethylene terephthalate film), etc.

  There are no particular restrictions on the solvent used when preparing the varnish, such as methyl ethyl ketone, acetone, methyl isobutyl ketone, 2-ethoxyethanol, toluene, butyl cellosolve, methanol, ethanol, 2-methoxyethanol, dimethylacetamide, dimethylformamide. , Methylpyrrolidone, cyclohexanone, and the like can be used. Of these, high-boiling solvents such as dimethylacetamide, dimethylformamide, methylpyrrolidone, and cyclohexanone are preferred for the purpose of improving coating properties. These solvents can be used alone or in combination of two or more.

  Although there is no restriction | limiting in particular in the compounding quantity of a solvent, It is preferable that the non volatile matter at the time of producing a varnish is 40-90 mass%, and it is more preferable that it is 50-80 mass%. If the non-volatile content is less than 40% by mass, the amount of solvent that volatilizes during varnish preparation is large, and a large amount of heat is required during drying, which tends to be disadvantageous in terms of cost. Since the viscosity is too high, the coating film may be defective.

  In consideration of the dispersibility of the filler component containing the high thermal conductivity particles, the varnish can be produced by a raking machine, a three roll, a bead mill, or a combination thereof. By mixing the filler component and the low molecular weight material in advance and then blending the high molecular weight material, the time required for mixing can be shortened. In addition, after forming the varnish, it is preferable to remove bubbles in the varnish by vacuum degassing.

  The thickness of the film is not particularly limited, but is preferably in the range of 25 to 250 μm. If the thickness is less than 25 μm, the stress relaxation effect tends to be poor, and if it exceeds 250 μm, the cost tends to increase. Further, when the film thickness is thinner than the circuit thickness, the embedding property tends to be lowered.

<Sealing film>
The sealing film of the present invention is formed by molding the above-described highly heat conductive resin composition of the present invention into a film shape.

  The sealing film of the present invention has high flexibility and fluidity in the B-stage state, has a low coefficient of linear expansion after curing, has excellent thermal conductivity, and has excellent protection characteristics on the surface of a semiconductor element. ing.

  The film for sealing of the present invention can be prepared by applying and drying the varnish of the high heat conductive resin composition of the present invention including the high heat conductive particles and the thermosetting epoxy resin composition. The varnish can be obtained by adding a solvent such as cyclohexanone and mixing with stirring.

  As a method for using the sealing film, a method similar to that used for a conventional solid or liquid sealing material can be considered. For example, after laminating a sealing film with a base material layer (base material film) on a substrate on which a semiconductor element or component is mounted using a hot plate press or a laminator, and then heat curing, the base material layer (base material layer) The material film) is peeled off or the base material layer (base material film) is peeled off, followed by heat curing. At this time, lamination can be performed so that no voids remain around the semiconductor element. However, in the case of flip chip mounting for high frequency applications, etc., it is also possible to laminate so as to leave a gap under the semiconductor element or component.

  It is preferable to apply pressure in the thickness direction to the sealing film obtained as described above. By doing in this way, both surfaces of a film are planarized and the adhesive strength of a film can be improved.

  The sealing film preferably has a transmittance of 10% or less in a wavelength region of 300 to 1100 nm. For that purpose, it preferably has a fine phase separation structure and is opaque. Accordingly, the sealing film preferably contains a colorant, and as the colorant, the above-described materials that absorb laser light, that is, pigments and dyes such as carbon black, graphite, titanium carbon, manganese dioxide, and phthalocyanine are used. Can be used. As for content of the coloring agent contained in the film for sealing, 0.1-10 mass% is preferable, More preferably, it is 0.5-2.0 mass%. When the content of the colorant is less than 0.1% by mass, the film is not colored and the visibility of the laser marking part is deteriorated. Conversely, when the content of the colorant exceeds 10% by mass, ionic impurities This causes problems such as an increase in film thickness, a decrease in film ductility, or a decrease in adhesive strength with semiconductor elements.

  Further, since the laser used for laser marking is often a YAG laser, it is preferable to use carbon black that is easily volatilized by the YAG laser as a colorant.

<Semiconductor device>
The semiconductor device of the present invention includes a semiconductor element, a semiconductor element, a substrate, a heat sink, and a support through at least one of the high thermal conductive resin composition, the adhesive film, and the sealing film of the present invention described above. 1 or 2 types selected from the group consisting of a metal plate and a ceramic plate.

  According to another aspect of the semiconductor device of the present invention, at least one of the high thermal conductive resin composition, the adhesive film, and the sealing film of the present invention described above is bonded to one surface or both surfaces of the semiconductor element. Alternatively, it is sealed.

  In any aspect, the semiconductor device of the present invention uses any one of the above-described highly heat conductive resin composition, adhesive film, and sealing film of the present invention. Excellent in reliability.

  The semiconductor device of the present invention is not particularly limited in its structure as long as it is manufactured using at least one of the high thermal conductive resin composition, the adhesive film, and the sealing film of the present invention described above. Examples thereof include a semiconductor device including a semiconductor element, a support member for the semiconductor element, and the adhesive film of the present invention in which the semiconductor element and the support member are joined.

  In a semiconductor device having a general structure, for example, a semiconductor element is bonded to a semiconductor element support member via the adhesive film of the present invention, and a connection terminal of the semiconductor element is electrically connected to an external connection terminal via a wire, It is sealed with a sealing material. In recent years, semiconductor devices having various structures have been proposed, and the use of the adhesive film of the present invention is not limited to this structure as long as the semiconductor element is in contact with the adhesive film.

  In the semiconductor device having a structure in which the semiconductor elements are bonded to each other, for example, the first-stage semiconductor element is bonded to the semiconductor element support member via the adhesive film of the present invention, and the present invention is further formed on the first-stage semiconductor element. The second-stage semiconductor element is bonded through the adhesive film. The connection terminals of the first-stage semiconductor element and the second-stage semiconductor element can be suitably used in a semiconductor device having a structure in which a plurality of semiconductor elements are stacked at the external connection end 9 lum via a wire.

  Moreover, the adhesive film of this invention can also be bonded together with a dicing tape, and can also be made into one sheet. Furthermore, a protective film can be attached as necessary. Thus, the semiconductor device manufacturing process can be simplified by previously laminating the dicing tape and the adhesive film.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not restrict | limited to these Examples, unless it deviates from the technical idea of this invention.

Example 1
84 parts by mass of an epoxy resin (1-{(3-methyl-4-oxiranylmethoxy) phenyl} -4- (4-oxiranylmethoxy) -1-cyclohexene) having a mesogenic group, catechol resorcinol novolak 22 parts by mass of resin, epoxy group-containing acrylic rubber (high molecular weight component, manufactured by Teikoku Chemical Industry Co., Ltd., trade name: HTR-860P-3, weight average molecular weight: 800,000, Tg: 12 ° C.) 12 parts by mass, 1-cyanoethyl -2-methylimidazole (curing accelerator, manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name: Curesol 2PZ-CN) 0.1 part by mass, γ-mercaptopropyltrimethoxysilane (coupling agent, manufactured by Nihon Unicar Co., Ltd., product) Name: A-189) 0.4 parts by mass and γ-ureidopropyltriethoxysilane (coupling agent, Nippon Unicar Co., Ltd.) Company-made, trade name: A-1160) Cyclohexanone is added to a composition consisting of 0.7 parts by mass, and further alumina (high thermal conductivity particles, manufactured by Tatsumori Co., Ltd., trade name: TS-AP7 (LV), average grain (Diameter: 5.3 μm) 1000 parts by mass were added.

  This was mixed with a bead mill, and cyclohexanone was further added to adjust the viscosity, followed by vacuum degassing to obtain a varnish. A varnish is applied on a polyethylene terephthalate film having a thickness of 38 μm as a carrier film, dried by heating at 120 ° C. for 15 minutes, and a film having a thickness of 50 μm is formed on the carrier film to produce an adhesive film. did. Moreover, SEM observation of the cured adhesive film was performed, and it was confirmed that the thermosetting epoxy resin composition and the high molecular weight component were phase-separated.

(Example 2)
Bisphenol F type epoxy resin (epoxy resin, epoxy equivalent: 156, manufactured by Toto Kasei Co., Ltd., trade name: YDF-8170C), 8 parts by mass, epoxy resin having a mesogenic group (1-{(3-methyl-4 -Oxiranylmethoxy) phenyl} -4- (4-oxiranylmethoxy) -1-cyclohexene) 75 parts by mass, catechol resorcinol novolak resin 22 parts by mass, epoxy group-containing acrylic rubber (high molecular weight component, Teikoku Sangyo Co., Ltd.) Product name: HTR-860P-3, weight average molecular weight: 800,000, Tg: 12 ° C., 12 parts by mass, and 1-cyanoethyl-2-methylimidazole (curing accelerator, manufactured by Shikoku Kasei Kogyo Co., Ltd., product Name: Curazole 2PZ-CN) 0.1 parts by mass, γ-mercaptopropyltrimethoxysilane (coupling agent, Nippon Unicar Co., Ltd., trade name: A-189) 0.4 parts by mass and γ-ureidopropyltriethoxysilane (coupling agent, Nihon Unicar Co., Ltd., trade name: A-1160) from 0.7 parts by mass Cyclohexanone was added to the resulting composition, and 1000 parts by mass of alumina (highly thermally conductive particles, manufactured by Tatsumori Co., Ltd., trade name: TS-AP7 (LV), average particle size: 5.3 μm) was further added.

  This was mixed with a bead mill, and cyclohexanone was further added to adjust the viscosity, followed by vacuum degassing to obtain a varnish. A varnish is applied on a polyethylene terephthalate film having a thickness of 38 μm as a carrier film, dried by heating at 120 ° C. for 15 minutes, and a film having a thickness of 50 μm is formed on the carrier film to produce an adhesive film. did. Moreover, SEM observation of the cured adhesive film was performed, and it was confirmed that the thermosetting epoxy resin composition and the high molecular weight component were phase-separated.

(Example 3)
Bisphenol F type epoxy resin (epoxy resin, epoxy equivalent: 156, manufactured by Toto Kasei Co., Ltd., trade name: YDF-8170C), 28 parts by mass, epoxy resin having mesogenic group (1-{(3-methyl-4 -Oxiranylmethoxy) phenyl} -4- (4-oxiranylmethoxy) -1-cyclohexene) 254 parts by mass, 77 parts by mass of catecholresorcinol novolac resin, phenol resin (curing agent, manufactured by DIC Corporation, trade name: LF-2882) 31 parts by mass, epoxy group-containing acrylic rubber (high molecular weight component, manufactured by Teikoku Chemical Industry Co., Ltd., trade name: HTR-860P-3, weight average molecular weight: 800,000, Tg: 12 ° C.) 70 parts by mass, 1-cyanoethyl-2-methylimidazole (curing accelerator, manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name: Curesol 2PZ CN) 0.6 parts by mass, γ-mercaptopropyltrimethoxysilane (coupling agent, Nippon Unicar Co., Ltd., trade name: A-189) 1.5 parts by mass and γ-ureidopropyltriethoxysilane (coupling agent) , Nippon Unicar Co., Ltd., trade name: A-1160) cyclohexanone is added to the composition consisting of 3.0 parts by mass, and alumina (high thermal conductivity particles, manufactured by Admatex Co., Ltd., trade name: AE2050, average particle diameter: 0.7 parts by weight) was added.

  This was mixed with a bead mill, and cyclohexanone was further added to adjust the viscosity, followed by vacuum degassing to obtain a varnish. A varnish is coated on a polyethylene terephthalate film having a thickness of 38 μm as a carrier film and dried by heating at 110 ° C. for 20 minutes to form a film having a thickness of 10 μm on the carrier film to produce an adhesive film. did. Moreover, SEM observation of the adhesive film was performed, and it was confirmed that the thermosetting epoxy resin composition and the high molecular weight component were phase-separated.

Example 4
Bisphenol F type epoxy resin (epoxy resin, epoxy equivalent: 156, manufactured by Toto Kasei Co., Ltd., trade name: YDF-8170C), 23 parts by mass, epoxy resin having a mesogenic group (1-{(3-methyl-4 -Oxiranylmethoxy) phenyl} -4- (4-oxiranylmethoxy) -1-cyclohexene) 207 parts by mass, catechol resorcinol novolak resin 63 parts by mass, phenol resin (curing agent, manufactured by DIC Corporation, trade name: LF-2882) 25 parts by mass, epoxy group-containing acrylic rubber (high molecular weight component, manufactured by Teikoku Chemical Industry Co., Ltd., trade name: HTR-860P-3, weight average molecular weight: 800,000, Tg: 12 ° C.) 57 parts by mass, 1-cyanoethyl-2-methylimidazole (curing accelerator, manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name: Curesol 2PZ CN) 0.5 parts by mass, γ-mercaptopropyltrimethoxysilane (coupling agent, Nippon Unicar Co., Ltd., trade name: A-189) 1.2 parts by mass and γ-ureidopropyltriethoxysilane (coupling agent) , Nippon Unicar Co., Ltd., trade name: A-1160) Cyclohexanone is added to the composition consisting of 2.4 parts by mass, and alumina (high thermal conductivity particles, manufactured by Admatex Co., Ltd., trade name: AE2050, average particle diameter: 0.7 parts by weight) was added.

  This was mixed with a bead mill, and cyclohexanone was further added to adjust the viscosity, followed by vacuum degassing to obtain a varnish. A varnish is applied as a carrier film on a polyethylene terephthalate film having a release thickness of 38 μm and dried by heating at 100 ° C. for 15 minutes to form a film having a thickness of 10 μm on the carrier film to produce an adhesive film. did. Moreover, SEM observation of the cured adhesive film was performed, and it was confirmed that the thermosetting epoxy resin composition and the high molecular weight component were phase-separated.

(Example 5)
Bisphenol F type epoxy resin (epoxy resin, epoxy equivalent: 156, manufactured by Toto Kasei Co., Ltd., trade name: YDF-8170C), 19 parts by mass, epoxy resin having a mesogenic group (1-{(3-methyl-4 -Oxiranylmethoxy) phenyl} -4- (4-oxiranylmethoxy) -1-cyclohexene) 168 parts by mass, catechol resorcinol novolak resin 48 parts by mass, phenol resin (curing agent, manufactured by DIC Corporation, trade name: LF-2882) 25 parts by mass, epoxy group-containing acrylic rubber (high molecular weight component, manufactured by Teikoku Chemical Industry Co., Ltd., trade name: HTR-860P-3, weight average molecular weight: 800,000, Tg: 12 ° C.) 48 parts by mass, 1-cyanoethyl-2-methylimidazole (curing accelerator, manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name: Curesol 2PZ CN) 0.5 part by mass, γ-mercaptopropyltrimethoxysilane (coupling agent, Nippon Unicar Co., Ltd., trade name: A-189) 1.0 part by mass and γ-ureidopropyltriethoxysilane (coupling agent) , Nippon Unicar Co., Ltd., trade name: A-1160) Cyclohexanone is added to the composition consisting of 2.0 parts by mass, and further alumina (high thermal conductivity particles, manufactured by Admatex Co., Ltd., trade name: AE2050, average particle diameter: 0.7 parts by weight) was added.

  This was mixed with a bead mill, and cyclohexanone was further added to adjust the viscosity, followed by vacuum degassing to obtain a varnish. A varnish is applied as a carrier film on a polyethylene terephthalate film having a release thickness of 38 μm and dried by heating at 100 ° C. for 15 minutes to form a film having a thickness of 10 μm on the carrier film to produce an adhesive film. did. Moreover, SEM observation of the cured adhesive film was performed, and it was confirmed that the thermosetting epoxy resin composition and the high molecular weight component were phase-separated.

(Example 6)
Bisphenol F type epoxy resin (epoxy resin, epoxy equivalent: 156, manufactured by Toto Kasei Co., Ltd., trade name: YDF-8170C), 13 parts by mass, epoxy resin having mesogenic group (1-{(3-methyl-4 -Oxiranylmethoxy) phenyl} -4- (4-oxiranylmethoxy) -1-cyclohexene) 117 parts by mass, catechol resorcinol novolac resin 43 parts by mass, epoxy group-containing acrylic rubber (high molecular weight component, Teikoku Sangyo Co., Ltd.) Made by company, trade name: HTR-860P-3, weight average molecular weight: 800,000, Tg: 12 ° C., 31 parts by mass, 1-cyanoethyl-2-methylimidazole (curing accelerator, manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name : Cureazole 2PZ-CN) 0.3 parts by mass, γ-mercaptopropyltrimethoxysilane (coupling agent, Nippon Unicar Co., Ltd., trade name: A-189) 0.7 parts by mass and γ-ureidopropyltriethoxysilane (coupling agent, Nihon Unicar Co., Ltd., trade name: A-1160) from 1.3 parts by mass Cyclohexanone was added to the resulting composition, and 1000 parts by mass of alumina (high thermal conductivity particles, Showa Denko KK, trade name: AS-50, average particle size: 9.0 μm) was further added.

  This was mixed with a bead mill, and cyclohexanone was further added to adjust the viscosity, followed by vacuum degassing to obtain a varnish. A varnish is applied on a polyethylene terephthalate film having a thickness of 38 μm as a carrier film, dried by heating at 120 ° C. for 15 minutes, and a film having a thickness of 70 μm is formed on the carrier film to produce an adhesive film. did. Moreover, SEM observation of the cured adhesive film was performed, and it was confirmed that the thermosetting epoxy resin composition and the high molecular weight component were phase-separated.

(Comparative Example 1)
Bisphenol F type epoxy resin (epoxy resin, epoxy equivalent: 156, manufactured by Toto Kasei Co., Ltd., trade name: YDF-8170C) 45 parts by mass, cresol novolac type epoxy resin (epoxy resin, epoxy equivalent: 209, manufactured by Toto Kasei Co., Ltd.) , Trade name: YDCN-700-10) 15 parts by weight, phenol resin (curing agent, manufactured by Mitsui Chemicals, trade name: XLC-LL), 50 parts by weight, epoxy group-containing acrylic rubber (high molecular weight component, Teikoku Chemical Industry) Product name: HTR-860P-3, weight average molecular weight: 800,000, Tg: 12 ° C., 12 parts by mass, 1-cyanoethyl-2-methylimidazole (curing accelerator, manufactured by Shikoku Kasei Kogyo Co., Ltd., product Name: 0.1 part by mass of cureazole 2PZ-CN), γ-mercaptopropyltrimethoxysilane (coupling) , Nippon Unicar Co., Ltd., trade name: A-189) 0.3 parts by mass and γ-ureidopropyltriethoxysilane (coupling agent, Nihon Unicar Co., Ltd., trade name: A-1160) 0.7 parts by weight Cyclohexanone is added to the composition comprising, and alumina (high thermal conductivity particles, manufactured by Tatsumori Co., Ltd., trade name: TS-AP7 (LV), specific gravity: 3.9, average particle size: 5.3 μm, thermal conductivity : 32 W / mK) 1000 parts by mass were added.

  This was mixed with a bead mill, and cyclohexanone was further added to adjust the viscosity, followed by vacuum degassing to obtain a varnish. A varnish was applied as a carrier film on a polyethylene terephthalate film having a thickness of 38 μm and subjected to release treatment, and dried by heating at 110 ° C. for 30 minutes to form a film having a thickness of 50 μm on the carrier film.

(Comparative Example 2)
171 parts by mass of bisphenol F type epoxy resin (epoxy resin, epoxy equivalent: 156, manufactured by Toto Kasei Co., Ltd., trade name: YDF-8170C), cresol novolac type epoxy resin (epoxy resin, epoxy equivalent: 209, manufactured by Toto Kasei Co., Ltd.) , Product name: YDCN700-10) 57 parts by mass, phenol resin (curing agent, manufactured by DIC Corporation, product name: LF-2882) 162 parts by mass, epoxy group-containing acrylic rubber (high molecular weight component, manufactured by Teikoku Chemical Industry Co., Ltd.) , Trade name: HTR-860P-3, weight average molecular weight: 800,000, Tg: 12 ° C., 70 parts by mass, 1-cyanoethyl-2-methylimidazole (curing accelerator, manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name: Cureazole 2PZ-CN) 0.6 part by mass, γ-mercaptopropyltrimethoxysilane (coupled Agent, Nippon Unicar Co., Ltd., trade name: A-189) 1.5 parts by mass and γ-ureidopropyltriethoxysilane (coupling agent, Nihon Unicar Co., Ltd., trade name: A-1160) 3.0 Cyclohexanone was added to the composition consisting of parts by mass, and 1000 parts by mass of alumina (high thermal conductivity particles, manufactured by Admatex, Inc., trade name: AE2050, average particle size: 0.7 μm) was further added.

  This was mixed with a bead mill, and cyclohexanone was further added to adjust the viscosity, followed by vacuum degassing to obtain a varnish. A varnish is applied as a carrier film on a polyethylene terephthalate film having a release thickness of 38 μm and dried by heating at 100 ° C. for 15 minutes to form a film having a thickness of 10 μm on the carrier film to produce an adhesive film. did.

(Comparative Example 3)
Bisphenol F type epoxy resin (epoxy resin, epoxy equivalent: 156, manufactured by Toto Kasei Co., Ltd., trade name: YDF-8170C) 140 parts by mass, cresol novolac type epoxy resin (epoxy resin, epoxy equivalent: 209, manufactured by Toto Kasei Co., Ltd.) , Trade name: YDCN700-10) 47 parts by mass, phenol resin (curing agent, manufactured by DIC Corporation, trade name: LF-2882) 132 parts by mass, epoxy group-containing acrylic rubber (high molecular weight component, manufactured by Teikoku Chemical Industry Co., Ltd.) , Trade name: HTR-860P-3, weight average molecular weight: 800,000, Tg: 12 ° C., 57 parts by mass, 1-cyanoethyl-2-methylimidazole (curing accelerator, manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name: Curazole 2PZ-CN) 0.5 part by mass, γ-mercaptopropyltrimethoxysilane (coupling Agent, Nihon Unicar Co., Ltd., trade name: A-189) 1.2 parts by mass and γ-ureidopropyltriethoxysilane (coupling agent, Nihon Unicar Co., Ltd., trade name: A-1160) 2.4 Cyclohexanone was added to the composition consisting of parts by mass, and 1000 parts by mass of alumina (high thermal conductivity particles, manufactured by Admatex, Inc., trade name: AE2050, average particle size: 0.7 μm) was further added.

  This was mixed with a bead mill, and cyclohexanone was further added to adjust the viscosity, followed by vacuum degassing to obtain a varnish. A varnish is applied as a carrier film on a polyethylene terephthalate film having a release thickness of 38 μm and dried by heating at 100 ° C. for 15 minutes to form a film having a thickness of 10 μm on the carrier film to produce an adhesive film. did.

(Comparative Example 4)
114 parts by mass of bisphenol F type epoxy resin (epoxy resin, epoxy equivalent: 156, manufactured by Toto Kasei Co., Ltd., trade name: YDF-8170C), cresol novolac type epoxy resin (epoxy resin, epoxy equivalent: 209, manufactured by Toto Kasei Co., Ltd.) , Trade name: YDCN700-10) 38 parts by mass, phenol resin (curing agent, manufactured by DIC Corporation, trade name: LF-2882), 108 parts by mass, epoxy group-containing acrylic rubber (high molecular weight component, manufactured by Teikoku Chemical Industry Co., Ltd.) , Trade name: HTR-860P-3, weight average molecular weight: 800,000, Tg: 12 ° C., 46 parts by mass, 1-cyanoethyl-2-methylimidazole (curing accelerator, manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name: Curazole 2PZ-CN) 0.4 parts by mass, γ-mercaptopropyltrimethoxysilane (coupled Agent, Nippon Unicar Co., Ltd., trade name: A-189) 1.0 part by mass and γ-ureidopropyltriethoxysilane (coupling agent, Nihon Unicar Co., Ltd., trade name: A-1160) 2.0 Cyclohexanone was added to the composition consisting of parts by mass, and 1000 parts by mass of alumina (high thermal conductivity particles, manufactured by Admatex, Inc., trade name: AE2050, average particle size: 0.7 μm) was further added.

  This was mixed with a bead mill, and cyclohexanone was further added to adjust the viscosity, followed by vacuum degassing to obtain a varnish. A varnish is applied as a carrier film on a polyethylene terephthalate film having a release thickness of 38 μm and dried by heating at 100 ° C. for 15 minutes to form a film having a thickness of 10 μm on the carrier film to produce an adhesive film. did.

(Comparative Example 5)
76 parts by mass of bisphenol F type epoxy resin (epoxy resin, epoxy equivalent: 156, manufactured by Toto Kasei Co., Ltd., trade name: YDF-8170C), cresol novolac type epoxy resin (epoxy resin, epoxy equivalent: 209, manufactured by Toto Kasei Co., Ltd.) , Trade name: YDCN700-10) 26 parts by mass, phenol resin (curing agent, manufactured by DIC Corporation, trade name: LF-2882) 72 parts by mass, epoxy group-containing acrylic rubber (high molecular weight component, manufactured by Teikoku Chemical Industry Co., Ltd.) , Trade name: HTR-860P-3, weight average molecular weight: 800,000, Tg: 12 ° C., 31 parts by mass, 1-cyanoethyl-2-methylimidazole (curing accelerator, manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name: Cureazole 2PZ-CN) 0.3 part by mass, γ-mercaptopropyltrimethoxysilane (coupling , Manufactured by Nihon Unicar Co., Ltd., trade name: A-189) 0.7 parts by mass and γ-ureidopropyltriethoxysilane (coupling agent, Nihon Unicar Co., Ltd., trade name: A-1160) 1.3 parts by mass Cyclohexanone was added to the composition, and 1000 parts by mass of alumina (high thermal conductivity particles, Showa Denko KK, trade name: AS-50, average particle size: 9.0 μm) was further added.

  This was mixed with a bead mill, and cyclohexanone was further added to adjust the viscosity, followed by vacuum degassing to obtain a varnish. A varnish is applied on a polyethylene terephthalate film having a thickness of 38 μm as a carrier film, dried by heating at 120 ° C. for 15 minutes, and a film having a thickness of 70 μm is formed on the carrier film to produce an adhesive film. did.

[Evaluation item]
(1) Storage elastic modulus of cured product The storage elastic modulus at 170 ° C. of the cured C-staged adhesive film was measured using a dynamic viscoelasticity measuring device (RVELOGY, DVE-V4) with a length of 20 mm, A cured product having a width of 4 mm is subjected to an automatic static load in a tensile mode, measured from −30 to 200 ° C. at a frequency of 10 Hz and a temperature rising rate of 5 ° C./min, and at 35 ° C. in a temperature-dependent measurement mode. The storage elastic modulus was measured.

(2) Adhesive strength Substrate (base material (manufactured by Hitachi Chemical Co., Ltd., MCL-E-679FG), resist ink (manufactured by Taiyo Ink Manufacturing Co., Ltd., PSR-4000 AUS308) coated on a hot plate at 120 ° C. )) A semiconductor element (5 mm square) was adhered on the top using an adhesive film, and cured at 140 ° C. for 2 hours and at 170 ° C. for 5 hours to obtain a sample. With respect to this sample, the shear strength at 260 ° C. after moisture absorption at 85 ° C./85% RH for 48 hours was measured using a universal bond tester (manufactured by Dage, series 4000).

(3) Film tackiness The tackiness was evaluated by a probe tack test according to JIS Z0237-1991. Using a tack tester (TAC-II, manufactured by Reska Co., Ltd.), the peel strength was defined as the tack force under the conditions of a probe diameter of 5.1 mm, a contact speed of 2 mm / second, and a peel speed of 10 mm / second. As the contact conditions, the contact force: 100 gf / cm ² and the contact time: 1 second were used as standard conditions, and the tack force at 60 ° C. was measured.

(4) Thermal conductivity Thermal conductivity was measured at 25 ° C. using a laser flash method (manufactured by NETZSCH, LFA447 Nanoflash) in the thickness direction of the adhesive film. As the measurement sample, an adhesive film whose thickness was adjusted to 200 μm or more and less than 400 μm by bonding was cured at 170 ° C. for 5 hours, and the cured product was cut into 10 mm square.

(5) Coefficient of linear expansion The coefficient of thermal expansion is from 25 ° C. to 150 ° C. at a rate of temperature increase of 5 ° C. per minute using a thermomechanical analyzer for a sample cured at 140 ° C. for 2 hours and 170 ° C. for 5 hours. The average thermal expansion coefficient was determined from the elongation.
The above evaluation results are shown in Table 1.

As shown in Table 1, the adhesive films of Examples 1 to 5 using the thermosetting epoxy resin composition containing the epoxy resin having mesogen and the curing agent for epoxy resin are the same as the adhesive films of Comparative Examples 1 to 5, In comparison, it is clear that the thermal conductivity is high. However, it can be confirmed that the tackiness of Example 1 is significantly inferior to that of Comparative Example 1. In Example 2 to which bisphenol F-type epoxy resin was added for the purpose of imparting tackiness, it was confirmed that the tackiness was sufficient even when compared with Comparative Example 1 and had high thermal conductivity.
Moreover, each Example and Comparative Example in each set of Example 3 and Comparative Example 2, Example 4 and Comparative Example 3, Example 5 and Comparative Example 4, Example 6 and Comparative Example 5 have the same high thermal conductivity. Although it is an example containing particles at the same filling rate, it can be seen that in each group, the thermal conductivity is improved by about 20% compared to the comparative example. In general, when the film thickness is about 10 μm, it is difficult to achieve high filling of the high thermal conductivity particles, and hence it is difficult to improve the thermal conductivity. In Examples 3 to 5, the thermal conductivity is increased while the film thickness is 10 μm. It was confirmed that it can be improved.

Claims (13)

1) high thermal conductivity particles, 2) thermosetting epoxy resin composition containing an epoxy resin monomer having mesogen and a curing agent for epoxy resin, and 3) high thermal conductivity containing at least a high molecular weight component having a weight average molecular weight of 10,000 or more. A resin composition comprising:
The high heat conductive resin composition, wherein the 2) thermosetting epoxy resin composition and the 3) high molecular weight component are phase-separated after curing. The high thermal conductive resin composition according to claim 1, wherein the epoxy resin monomer is an epoxy resin monomer represented by the following general formula (1).
E-MS-ME ... General formula (1)
(However, E represents an epoxy group, M represents a mesogen, and S represents a spacer portion) The 3) high molecular weight component is dissolved with the 2) thermosetting epoxy resin composition before curing, and has a glass transition temperature of 30 ° C. or less having a weight average molecular weight of 100,000 or more that phase-separates into an island shape after curing. A high molecular weight component,
Said 1) high thermal conductivity particle is 40-90 volume% of the whole, and said 3) 5-50 mass parts of said high molecular weight component is contained with respect to 100 mass parts of thermosetting epoxy resin composition. The high thermal conductive resin composition according to claim 1, wherein:   Furthermore, the highly heat conductive resin composition of any one of Claims 1-3 containing the pigment, dye, and compound which absorb a laser beam. A cured resin product obtained by curing the thermosetting resin composition according to any one of claims 1 to 4,
It has an anisotropic structure consisting of a crystal phase or a liquid crystal phase, the maximum value of the diameter of the anisotropic structural unit is 400 nm or more, and the proportion of the anisotropic structure contained in the resin component is 25% by volume or more. A cured product of high thermal conductive resin, characterized by   An adhesive film formed by molding the high thermal conductive resin composition according to any one of claims 1 to 4 into a film shape.   An adhesive film obtained by applying pressure in the thickness direction to the adhesive film according to claim 6.   The adhesive film according to claim 7, wherein pressure is applied to the adhesive film under heating by pressing or roll processing, followed by cooling.   A sealing film formed by molding the high thermal conductive resin composition according to any one of claims 1 to 4 into a film shape.   A film for sealing obtained by applying pressure in the thickness direction to the film for sealing according to claim 9.   A film for sealing, wherein the film for cooling according to claim 9 is cooled by applying pressure under heating by press processing or roll processing.   The high thermal conductive resin composition according to any one of claims 1 to 4, the adhesive film according to any one of claims 6 to 8, and the seal according to any one of claims 9 to 11. A semiconductor element and one or two kinds selected from the group consisting of a semiconductor element, a substrate, a heat sink, a support, a metal plate, and a ceramic plate are stacked through at least one of the stop films. A semiconductor device characterized by comprising:   The high thermal conductive resin composition according to any one of claims 1 to 4, the adhesive film according to any one of claims 6 to 8, and the seal according to any one of claims 9 to 11. A semiconductor device, wherein at least one of the stop films is bonded or sealed to one or both sides of a semiconductor element.